Polyolefins stabilized with alkyl-4-hydroxyphenyl carbamates



United States Patent Office 3,367,908 Patented Feb. 6, 1968 3,367,908 POLYOLEFINS STABILIZED WITH ALKYL-4- HYDROXYPHENYL CARBAMATES Janet Brooks Peterson, Yonkers, and Martin Dexter, Briarcliff Manor, N.Y., assignors to Geigy Chemical Corporation, Greenburgh, N.Y., a corporation of Delaware No Drawing. Original application Sept. 17, 1962, Ser. No. 224,604, new Patent No. 3,303,211, dated Feb. 7, 1967. Divided and this application Oct. 31, 1966, Ser. No.

12 Claims. (Cl. 26045.85)

This application is a division of co-pending application Ser. No. 224,604, filed Sept. 17, 1962, now US. Patent 3,303,211.

This invention relates to the stabilization of polypropylene and other unstable organic material with phenols having a carbamate group in particular with stabilizers derived from certain 3-t-lower alkyl-4-hydroxyphenyl carbamates. The invention also relates to a method of preparing stabilized polypropylene and/ or other organic material subject to degradation.

More specifically, the invention pertains to stabilization of polypropylene and/or other organic material normally subject to oxidative deterioration with a stabilizer of the Formula I:

I wherein R and R are the same as above, and

B is a member selected from the group consisting of and wherein R is lower alkyl or hydrogen, and

R is lower alkylene.

In the foregoing Formula I,

'R and R may be methyl, ethyl, propyl, butyl, pcntyl,

hexyl, R may be methyl, ethyl, propyl, butyl, pentyl, hexyl,

heptyl, octyl,

I R may be methylene, ethylene, propylene, butylene, pentylene, hexylene, A may be alkyl of l to 24 carbon atoms, examples of alkyl groups being the same as R and also nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, nonadecyl, eicosyl, docosyl, tricosyl, tetracosyl; examples of lower alkylphenyl are tolyl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, hexylphenyl.

It is an object of the invention to provide stable organic material, e.g., stable polyolefinic material, preferably stable polypropylene and polyethylene. Preferably the polyolefins are of high molecular weight, e.g., above 1000 into the hundreds of thousands range. The polyethylenes may be of high density, medium density or low density class.

Polymeric materials such as the foregoing find use as thermoplastic molding or coating agents. Moreover, because of their high dielectric strength and their resistance to water, they are particularly useful as insulators or dielectrics in condensers and other such equipment. It is known that these polyolefins, e.g. polyethylene and polypropylene, are attacked by oxygen, particularly when exposed to the atmosphere and at elevated temperatures. For example, during use or manufacture the desirable properties of the polyolefins may be impaired due to oxidative deterioration. Such degradation causes loss in dielectric properties, discoloration, embrittlement, gelation, etc. Thermal degradation is also checked by the invention.

Not only homopolymeric material, but also copolymers and physical mixtures thereof are stabilized according to the present invention. For example, high impact polystyrene containing copolymers of butadiene and styrene are stabilized according to the invention.

The invention is also useful in stabilizing lubricating oils of various types including aliphatic esters such as, e.g. dihexyl azelate, di-(2 ethylhexyl)azelate, di-(3,5,5- trimethylhexyl)glutarate, di-( 3,5 ,itrimethylpentyl glutarate, di-(Zethylhexyl)pimelate, di-(Z-ethylhexyl)adipate, diisoamyl adi-pate, triamyl tricarballylate, pentaerythritol tetracaproate, dipropylene glycol di-pelargonate, 1,5-pentanediol-di (Z-ethylhexanoate), etc.

The present invention also relates to the stabilizing of fatty materials including oils of animal and vegetable origin which tend to deteriorate on standing and exposure to atmospheric oxygen. Among the edible fats and oils within the scope of the present invention are: linseed oil, menhaden oil, cod liver oil, castor oil, olive oil, rapeseed oil, coconut oil, palm oil, corn oil, sesame oil, peanut oil, cotton seed oil, butter, fat, lard, beef tallow, etc. Other oils and fats which deteriorate on standing and exposure to oxygen in the air or oxygen at elevated temperatures are all Within the scope of the present invention.

Within the scope of the invention also are saturated and unsaturated hydrocarbons which tend to deteriorate on storage such as, e.g., gasolines, both natural and synthetic, in particular, saturated and unsaturated gasolines, etc.; jet fuel; diesel oil; mineral oil; fuel oil; drying oil; waxes; resins; etc. Such hydrocarbons are protected against gum formation, discoloration and other deterioration with the stabilizers of the present invention.

It is furthermore an object of the present invention to provide novel substituted stabilizers of the formula I which are versatile and effective stabilizers in at least a single class of the foregoing organic materials which are normally subject to deterioration caused by exposure to light and/or heat and/or oxygen, etc.

Particularly preferred stabilizers of the invention are 3-t-butyl-4-hydroxyphenyl-N-(n octadecylcarbamate and 2-t-butyl 4 hydroxypheny l- N n octadecyl carbamate which are especially useful in stabilizing polyolefinic material, e.g. polypropylene and polyethylene.

It is understood that the stabilizers of the invention are not necessarily of equivalent potency. The specific stabilizer most useful to a given unstable material will depend upon several factors, for its advantages. Availability and cost of raw materials for the manufacture of the stabilizer and effective inhibitory action of the stabilizer including duration and degree of activity are among the factors which control the choice of a specific stabilizer for a specific substrate which is normally subject to deterioration. Toxicity, color, .stability to light and/ or heat and solubility are also important factors.

In general, stabilizers of the invention are employed in a concentration of from about 0.001% to about by weight, preferably from about 0.01% to about 1% by weight. The specific concentration used varies with the substrate and the stabilizer, but the following ranges are preferred.

Concentrations of about 0.001% to about 1% by weight for the stabilizer in polyethylene are useful. In polypropylene from about 0.05% to about 1% by weight of stabilizer is especially useful. In mineral oils, concentrations of from about 0.005% to about 1% by weight of stabilizer are used. Gasolines are stabilized with from about 0.001% to about 0.1% by weight of stabilizer, preferably about 0.05% by weight. Fatty material of animal origin such as lard is stabilized with from about 0.001% to about 0.1% by weight of stabilizer. Oils of vegetable origin such as cotton seed oil are similarly stabilized with from about 0.001% to about 0.1% by weight of stabilizer.

Hydrocarbon material such as cycloolefins, eg. cyclohexene, is advantageously stabilized with from about 0.001% to about 1% by weight of the stabilizers of the present invention. Similar concentrations of stabilizer are used to stabilize aldehydes such as, e.g., about 0.01% by weight in heptaldehyde. High temperature lubricants which are essentially synthetic esters of alkanoic acids, e.g. trimethylol propane tripelargonate, and diisoamyladipate, are stabilized with from about 0.5% to about 5%, preferably about 2%, by weight of a stabilizer according to the invention.

The compounds of this invention may be used also to stabilize organic material in combination with other additive agents such as, e.g., antioxidants, pourpoint depres- I sants, corrosion and rust inhibitors, dispersing agents, demulsifiers, antifoaming agents, carbon black, accelerators and other chemicals used in rubber compounding, plasticizers, color stabilizers, heat stabilizers, ultraviolet absorbers, dyes, pigments, metal chelating agents, etc.

A particularly useful stabilizer system in some cases comprises a stabilizer of the Formula I and di-laurylbeta thio di propionate (hereinafter referred to as DLTDP). Generally from about 0.005% to about (based on the stabilized composition) by weight of DLTDP and other stabilizers, e.g. of the Formula I, are employed. Polypropylene is advantageously stabilized with about 0.1% to 0.5% by weight of DLTDP and 0.1% to 0.5 by weight of a stabilizer of the Formula I.

In place of DLTDP, other similar diesters are usefully employed with the stabilizers of the Formula I for stabilization of organic material, e.g., polypropylene. Such diesters as the following are useful:

l ormcm) coom wherein n is a small number, e.g. 1 or 2; and

R and R are each independently an alkyl group, e.g. having 8 to 24 carbon atoms, such as octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, eicosyl, heneicosyl, tricosyl, tetracosyl.

The stabilizer compounds of the Formula I are preparedby reaction of the appropriate alkylhydroquinone compound with the appropriate isocyanate to form the desired alkylhydroxyphenyl N-substituted carbamate.

The following examples are illustrative of the invention only, and there is no intention to limit the scope of the invention thereto. In the following examples parts are by weight, unless otherwise specified, and temperature is in degrees centigrade. The relationship between parts by weight and parts by volume is as that of grams to cubic centimeters.

EXAMPLE 1 3,5-di-t-butyl-4-hydroxyphenyl N- (n-octadecyl) carbamate n-Octadecyl isocyanate (8.88 parts), 6.66 parts of 2,6- di-t-butyl-1,4-hydroquinone, 35 parts of n-hexane and 5 drops of pyridine are refluxed together for 2 hours. The solution is cooled and allowed to stand at room temperature, and a small amount of insoluble material is filtered off. The filtrate is distilled in vacuo to remove the hexane and the waxy residue is broken up and slurried in methanol. The white, crystalline solid is filtered, washed with methanol, and dried, and 11.3 parts are recrystallized from a mixture of methanol and a small amount of petroleum ether. In this manner, 9.5 parts of 3,5-di-t-butyl- 4-hydroxyphenyl N-(n-octadecyl) carbamate are obtained as white, crystalline powder, M.P. 5 05 1 Analysis.Calculated for C H O N. C, 76.54%; H, 11.49%; N, 2.71%. Found: C, 76.42%; H, 11.62%; N, 3.00%.

In a similar manner by using 2,6-di-t-octyl-1,4-hydroquinone, then 3,5-di-t-octyl-4-hydroxyphenyl N-(noctadecyl)carbamate is obtained.

EXAMPLE 2 3-t-butyl-4-hydroxyphenyl N-(n 0ctadecyl)carbamate(a) and 2-t-butyl-4-hydr0xyphenyl N-(n octadeeyl) carbamate(b) (a) n-Octadecyl isocyanate (8.88 parts), 4.98 parts of 2-t-butyl-1,4-hydroquinone, 50 parts of dioxane and 6 drops of pyridine are refluxed together for 4 hours. The solution is cooled and allowed to stand at room temperature and a small amount of insoluble material is filtered off. The filtrate is evaporated to dryness in vacuo, and the solidified residue (15.5 parts) is taken up in 20 parts of methanol. The methanol slurry is cooled in an ice-water bath, filtered and triturated and washed several times with cold methanol. The methanol filtrate and washes are combined and saved. The dried solid (3.5 parts) is recrystallized from a mixture of petroleum ether and nhexane (2:1 by volume), and 1.8 parts of 3-t-butyl-4- hydroxyphenyl N-(n-octadecyl) carbamate are obtained as a White, crystalline powder, M.P. 88-93".

Analysis.-Calculated for C H O N: C, 75.44%; H, 11.13%; N, 3.03%. Found: C, 75.41%; H, 11.17%; N, 2.79%.

(b) The methanol is removed in vacuo from the combined filtrate washings which had been saved [see above (a)], and the crystalline residue (8 parts) is triturated, filtered and washed with petroleum ether. The solid (2.5 parts is recrystallized from a mixture of petroleum ether and n-hexane (3:1 by volume) and 2 parts of Z-t-butyl- 4-hydroxyphenyl N-(n-octadecyl) carbamate are obtained as a white, crystalline powder, M.P. 75-795".

Analysis.Calculated for C H O N: C, 75.44%; H, 11.13%; N, 3.03%. Found: C, 75.41%; H, 11.05%; N, 2.96%.

EXAMPLE 3 Di (3,5 -di-t-butyl-4-hydr0xy phenyl N ,N -(4-methyll ,3 -phenylene dicarbam are 4-methyl-m-phenylenediisocyanate (3.48 parts), 9 parts 2,6-di-t-butyl-1,4-hydroquinone, 35 parts of n-hexane and 5 drops of pyridine are refluxed together for /2 hour. The solution is cooled to room temperature and a small amount of insoluble material is filtered off. The filtrate, from which the product tends to oil out, is diluted somewhat with n-hexane and a few parts of benzene, heated to boiling, then cooled, the supernatant solution poured off, and the residual syrup taken up in 25-35 parts of benzene. The mixture is warmed to effect complete solution and the product is reprecipit-ated by the addition of petroleum ether. The finely divided solid is filtered, washed with petroleum ether, and dried, and 6 parts are recrystallized from a mixture of hexane and ethyl acetate (7:1 by volume). After a long period of standing, 1.5 parts of di- 3,5 -di-t-butyl 4 hydroxypenyl) -N,N4 (4-methyl-1,3-phenylene)dicarbamate are obtained as white crystals, M.P. 13514l. I

A nalysis.-Calculated for gs'fHfioo fiNz: C, 71.81% H, 8.15%; N, 4.53%. Found? C, 71. 94%; H, 7.95%; N, 4.39%.

EXAMPLE 4 Di(3,5-di-t-bulyl-4-hydroxyphenyl) methylcrzc-N,N'-

(di-p,p-phenylen e) dicarbamate Metl'1ylene-p-phenylene diisocyanate (5.01 parts), 8.88 parts of 2,6-di-t-1,4-butylhydroquinone, 55 parts of henzene and 5 drops of pyridine arerefluxed together for 3 /4 hours. The clear solution is cooled shortly to room temperature and allowed to stand overnight. The precipitated white, crystalline solid is filtered, washed with benzene, and dried. In .this way,13.5 parts of di(3,5-di-tbutyl 4-hydroxyphenyl)methylene-N,N'-p,p'-phenylene) dicarbamate are obtained, M. P. l76l77.5.

Analysis.'Calculated for C H O N C, 74.32%; H,

7.83%; N, 4.03%. Found: C, 74.33%; H, 8.06%; N,

. EXAMPLE 5 3,5-di-t-buIyl4-hydroxyphenyl N (0-t0lyI) carbamate EXAMPLE 6 Stabilization of polypropylene 'Unstabilized polypropylene powder (Hercules PRO- FAX 6501) is thoroughly blended with 0.5% by weight of 3-t-butyl-4-hydroxyphenyl N-(n-octadecyl)carbamate. The blended material is then milled on a two roller mill at 182 for 5 minutes, after which time the stabilized polypropylene is sheeted from the mill and allowed to cool.

The milled polypropylene sheet is then cut into small pieces and pressed for 7 minutes on a hydraulic press at 218 and 2000 pounds per square inch pressure. The resultant sheet of mil thickness is then tested for resistance to accelerated aging in a forced draft oven at 149. The resultant composition of 0.5% by weight of 3- t butyl-4-hydroxyphenyl N-n-octadecyl)carbamate and polypropylene is stabilized against oxidative deterioration for more than 500 hours. The unstabilized polypropylene deteriorates after only 3 hours.

In like manner as in this example, stabilized compositions of polypropylene are prepared having 0.5% by weight of each of the following:

3,5 di t-butyl-4-hyd-roxyphenyl N-(n-octadecyl)carbamate.

2 t butyl-4-hydroxyphenyl N-(n-octadecyl)carbamate.

Di (3,5 di-t-butyl-4-hydroxyphenyl)N,N'-(4-methyl- 1,3-phenylene)dicarbamate.

Di(3,5 di t-butyl-4-hydroxyphenyl)1nethylene-N,N-

di-p,-p-phenylene) dicarbamate.

3,5 di t-butyl-4-hydroxyphenyl N-(o-tolyl)carbamate.

Stabilization of polypropylene In a similar manner as in this example, stable compositions of polypropylene are prepared with 0.1% by weight of a compound according to each of the preced- 6 ing examples in Part II, together with 0.5% by weight of di-lanryl- -thio-dipropionate. In some cases the improvement is so remarkable that a synergistic effect is observed in the oven-aging test.

What is claimed is:

1. A composition of matter stabilized against deterioration which comprises polyolefin normally subject to deterioration and a stabilizing amount of a stabilizer compound of the formula:

wherein R is an alkyl group having 3 to 8 carbon atoms,

R is a member selected from the group consisting of hydrogen and an alkyl group having 1 to 8 carbon atoms,

A is a member selected from the group consisting of alkyl having 1 to 24 carbon atoms, lower alkylphenyl, and the radical of the formula:

R and R are the same 'as above, and B is a member selected from the group consisting of wherein and wherein R is a member selected from the group consisting of lower alkyl and hydrogen, and R is lower alkylene.

2. A composition of matter as claimed in claim 1 wherein the polyolefin is polypropylene.

3. A composition of matter as claimed in claim 2 wherein the stabilizer compounds is 3,5-di-t-butyl-4-l1ydroxyphenyl N-(n-octadecyl)'carbamate.

4. A composition of matter as claimed in claim 2 wherein the stabilizer compound is 3-t-butyl-4-'hydroxyphenyl N-(n-octadecyl)carbamate.

5. A composition of matter as claimed in claim 2 wherein the stabilizer compound is 2-t-butyl-4-'hydroxyphenyl N-(n-octadecyl)carbamate.

6. A composition of matter as claimed in claim 2 wherein the stabilizer compound is di(3,5-di-t-butyl-4-hydroxyphenyl)N,N' (1 methyl 1,3 phenylene) dicarbamate.

7. A composition of matter as claimed in claim 2 wherein the stabilizer compounds is di( 3,5-di-t-butyl-4 hydroxyphenyl)methylene N,N (di-p,p'-phenylene)dicarbamate.

8. A composition of matter as claimed in claim 2 wherein the stabilizer compounds is 3,5-di-t-butyl-4-hydroxyphenyl N-(o-tolyl)carbamate.

9. A composition of matter which comprises a polyolefin normally subject to deterioration and a stabilizer system consisting essentially of (a) a stabilizer of the formula:

k R: wherein R and R are the same as above, and B is a member selected from the group consisting of and wherein. n

Risa member selected from the group consisting of lower alkyl and hydrogen, and R is lower alkylene,

(b) a stabilizer of the formula:

OH2(CII2)nCOOR3 IHflCIIZX-lC O 0 B4 wherein n is a member selected from the group consisting of 1 and 2, and R and R are each independently an alkyl group having 8 to 24 carbon atoms.

10. A composition of matter as claimed in claim 9 wherein the proportions by weight of component (a) to component (b) are from about 1:5 to about 5:1.

11. A composition of matter as claimed in claim -9 wherein said polyolefin is polypropylene.

12. A composition of matter as claimed in claim 9 wherein the polyolefin is polypropylene and the stabilizer system comprises a mixture of 3-t butyl-4-hydroxyphenyl N- (n-octadecyl)carbamate and di-lauryl-fi-thiodipropionate.

References Cited FOREIGN PATENTS 851,670 10/ 1960 Great Britain.

DONALD E. CZAJA, Primary Examiner.

V. P. HOKE, Assistant Examiner. 

1. A COMPOSITION OF MATTER STABILIZED AGAINST DETERIORATION WHICH COMPRISES POLYOLEFIN NORMALLY SUBJECT TO DETERIORATION AND A STABILIZING AMOUNT OF A STABILIZER COMPOUND OF THE FORMULA:
 9. A COMPOSITION OF MATTER WHICH COMPRISES A POLYOLEFIN NORMALLY SUBJECT TO DETERIORATION AND A STABILIZER SYSTEM CONSISTING ESSENTIALLY OF (A) A STABILIZER OF THE FORMULA 